We have already reported that copper and calcium dipivaloylmethanates [Cu(DPM)2 and Ca(DPM)2 ] reacts selectively and stoichiometrically with surface hydroxyl groups (OH) on SiO2. In order to clarify the structure of the adsorbed species and the origin of the reaction between M(DPM)2 (M=Cu and Ca) and OH groups, the surface adsorbed species are studied by infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and the extended X-ray absorption fine structure (EXAFS). As a result, it was found that H from surface OH has moved into M(DPM)2 after the adsorption, where the four oxygen coordinated structure around Cu still exists in the adsorbed Cu(DPM)2. Introducing water vapor at 673 K to this surface results in the removal of ligand DPM from the adsorbed Cu(DPM)2. At 673 K, Cu atoms decomposed from the adsorbates aggregated on the surface. This fact supports that the interaction between the adsorbed Cu(DPM)2 and SiO2 surface is originated from that between the ligands and the surface.